Photonic Crystal Hydrogel Enhanced Plasmonic Staining for Multiplexed Protein Analysis

Plasmonic nanoparticles are commonly used as optical transducers in sensing applications. The optical signals resulting from the interaction of analytes and plamsonic nanoparticles are influenced by surrounding physical structures where the nanoparticles are located. This paper proposes inverse opal photonic crystal hydrogel as 3D structure to improve Raman signals from plasmonic staining. By hybridization of the plasmonic nanoparticles and photonic crystal, surface‐enhanced Raman spectroscopy (SERS) analysis of multiplexed protein is realized. It benefits the Raman analysis by providing high‐density “hot spots” in 3D and extra enhancement of local electromagnetic field at the band edge of PhC with periodic refractive index distribution. The strong interaction of light and the hybrid 3D nanostructure offers new insights into plasmonic nanoparticle applications and biosensor design.     

Ordered Arrangement and Optical Properties of Silica‐Stabilized Gold Nanoparticle–PNIPAM Core–Satellite Clusters for Sensitive Raman Detection

Gold–polymer hybrid nanoparticles attract wide interest as building blocks for the engineering of photonic materials and plasmonic (active) metamaterials with unique optical properties. In particular, the coupling of the localized surface plasmon resonances of individual metal nanostructures in the presence of nanometric gaps can generate highly enhanced and confined electromagnetic fields, which are frequently exploited for metal‐enhanced light–matter interactions. The optical properties of plasmonic structures can be tuned over a wide range of properties by means of their geometry and the size of the inserted nanoparticles as well as by the degree of order upon assembly into 1D, 2D, or 3D structures. Here, the synthesis of silica‐stabilized gold–poly(N‐isopropylacrylamide) (SiO₂‐Au‐PNIPAM) core–satellite superclusters with a narrow size distribution and their incorporation into ordered self‐organized 3D assemblies are reported. Significant alterations of the plasmon resonance are found for different assembled structures as well as strongly enhanced Raman signatures are observed. In a series of experiments, the origin of the highly enhanced signals can be assigned to the interlock areas of adjacent SiO₂‐Au‐PNIPAM core–satellite clusters and their application for highly sensitive nanoparticle‐enhanced Raman spectroscopy is demonstrated.     

Plasmonic Chirality and Circular Dichroism in Bioassembled and Nonbiological Systems: Theoretical Background and Recent Progress

Nature is chiral, thus chirality is a key concept required to understand a multitude of systems in physics, chemistry, and biology. The field of optics offers valuable tools to probe the chirality of nanosystems, including the measurement of circular dichroism, the differential interaction strength between matter and circularly polarized light with opposite helicity. Simultaneously, the use of plasmonic systems with giant light-interaction cross-sections opens new paths to investigate and manipulate systems on the nanoscale. Consequently, the interest in chiral plasmonic and hybrid systems has continually grown in recent years, due to their potential applications in biosensing, polarization-encoded optical communication, polarization-selective chemical reactions, and materials with polarization-dependent light–matter interaction. Experimentally, chiral properties of nanostructures can be either created artificially using modern fabrication techniques involving inorganic materials, or borrowed from nature using bioassembly or biomolecular templating. Herein, the recent progress in the field of plasmonic chirality is summarized, with a focus on both the theoretical background and the experimental advances in the study of chirality in various systems, including molecular-plasmonic assemblies, chiral plasmonic nanostructures, chiral assemblies of interacting plasmonic nanoparticles, and chiral metal metasurfaces and metamaterials. The growth prospects of this field are also discussed.     

Nanostructured Dielectric Fractals on Resonant Plasmonic Metasurfaces for Selective and Sensitive Optical Sensing of Volatile Compounds

Advances in the understanding and fabrication of plasmonic nanostructures have led to a plethora of unprecedented optoelectronic and optochemical applications. Plasmon resonance has found widespread use in efficient optical transducers of refractive index changes in liquids. However, it has proven challenging to translate these achievements to the selective detection of gases, which typically adsorb non‐specifically and induce refractive index changes below the detection limit. Here, it's shown that integration of tailored fractals of dielectric TiO₂ nanoparticles on a plasmonic metasurface strongly enhances the interaction between the plasmonic field and volatile organic molecules and provides a means for their selective detection. Notably, this superior optical response is due to the enhancement of the interaction between the dielectric fractals and the plasmonic metasurface for thickness of up to 1.8 μm, much higher than the evanescent plasmonic near‐field (≈30 nm) . Optimal dielectric–plasmonic structures allow measurements of changes in the refractive index of the gas mixture down to <8 × 10^?6 at room temperature and selective identification of three exemplary volatile organic compounds. These findings provide a basis for the development of a novel family of dielectric–plasmonic materials with application extending from light harvesting and photocatalysts to contactless sensors for noninvasive medical diagnostics.     

Many‐Body Complexes in 2D Semiconductors

2D semiconductors such as transition metal dichalcogenides (TMDs) and black phosphorus (BP) are currently attracting great attention due to their intrinsic bandgaps and strong excitonic emissions, making them potential candidates for novel optoelectronic applications. Optoelectronic devices fabricated from 2D semiconductors exhibit many‐body complexes (exciton, trion, biexciton, etc.) which determine the materials optical and electrical properties. Characterization and manipulation of these complexes have become a reality due to their enhanced binding energies as a direct result from reduced dielectric screening and enhanced Coulomb interactions in the 2D regime. Furthermore, the atomic thickness and extremely large surface‐to‐volume ratio of 2D semiconductors allow the possibility of modulating their inherent optical, electrical, and optoelectronic properties using a variety of different environmental stimuli. To fully realize the potential functionalities of these many‐body complexes in optoelectronics, a comprehensive understanding of their formation mechanism is essential. A topical and concise summary of the recent frontier research progress related to many‐body complexes in 2D semiconductors is provided here. Moreover, detailed discussions covering the aspects of fundamental theory, experimental investigations, modulation of properties, and optoelectronic applications are given. Lastly, personal insights into the current challenges and future outlook of many‐body complexes in 2D semiconducting materials are presented.     

Ultrathin Ruddlesden–Popper Perovskite Heterojunction for Sensitive Photodetection

Thanks to their unique optical and electric properties, 2D materials have attracted a lot of interest for optoelectronic applications. Here, the emerging 2D materials, organic–inorganic hybrid perovskites with van der Waals interlayer interaction (Ruddlesden–Popper perovskites), are synthesized and characterized. Photodetectors based on the few‐layer Ruddlesden–Popper perovskite show good photoresponsivity as well as good detectivity. In order to further improve the photoresponse performance, 2D MoS₂ is chosen to construct the perovskite–MoS₂ heterojunction. The performance of the hybrid photodetector is largely improved with 6 and 2 orders of magnitude enhancement for photoresponsivity (10⁴ A W^?1) and detectivity (4 × 10¹⁰ Jones), respectively, which demonstrates the facile charge separation at the interface between perovskite and MoS₂. Furthermore, the contribution of back gate tuning is proved with a greatly reduced dark current. The results demonstrated here will open up a new field for the investigation of 2D perovskites for optoelectronic applications.     

Two‐Dimensional Materials for Halide Perovskite‐Based Optoelectronic Devices

Halide perovskites have high light absorption coefficients, long charge carrier diffusion lengths, intense photoluminescence, and slow rates of non‐radiative charge recombination. Thus, they are attractive photoactive materials for developing high‐performance optoelectronic devices. These devices are also cheap and easy to be fabricated. To realize the optimal performances of halide perovskite‐based optoelectronic devices (HPODs), perovskite photoactive layers should work effectively with other functional materials such as electrodes, interfacial layers and encapsulating films. Conventional two‐dimensional (2D) materials are promising candidates for this purpose because of their unique structures and/or interesting optoelectronic properties. Here, we comprehensively summarize the recent advancements in the applications of conventional 2D materials for halide perovskite‐based photodetectors, solar cells and light‐emitting diodes. The examples of these 2D materials are graphene and its derivatives, mono‐ and few‐layer transition metal dichalcogenides (TMDs), graphdiyne and metal nanosheets, etc. The research related to 2D nanostructured perovskites and 2D Ruddlesden–Popper perovskites as efficient and stable photoactive layers is also outlined. The syntheses, functions and working mechanisms of relevant 2D materials are introduced, and the challenges to achieving practical applications of HPODs using 2D materials are also discussed.     

In‐Plane Isotropic/Anisotropic 2D van der Waals Heterostructures for Future Devices

Mono‐ to few‐layers of 2D semiconducting materials have uniquely inherent optical, electronic, and magnetic properties that make them ideal for probing fundamental scientific phenomena up to the 2D quantum limit and exploring their emerging technological applications. This Review focuses on the fundamental optoelectronic studies and potential applications of in‐plane isotropic/anisotropic 2D semiconducting heterostructures. Strong light–matter interaction, reduced dimensionality, and dielectric screening in mono‐ to few‐layers of 2D semiconducting materials result in strong many‐body interactions, leading to the formation of robust quasiparticles such as excitons, trions, and biexcitons. An in‐plane isotropic nature leads to the quasi‐2D particles, whereas, an anisotropic nature leads to quasi‐1D particles. Hence, in‐plane isotropic/anisotropic 2D heterostructures lead to the formation of quasi‐1D/2D particle systems allowing for the manipulation of high binding energy quasi‐1D particle populations for use in a wide variety of applications. This Review emphasizes an exciting 1D–2D particles dynamic in such heterostructures and their potential for high‐performance photoemitters and exciton–polariton lasers. Moreover, their scopes are also broadened in thermoelectricity, piezoelectricity, photostriction, energy storage, hydrogen evolution reactions, and chemical sensor fields. The unique in‐plane isotropic/anisotropic 2D heterostructures may open the possibility of engineering smart devices in the nanodomain with complex opto‐electromechanical functions.     

Organic Microcavity Photodiodes

The interaction of light and matter lies at the heart of the principle of optoelectronic devices. By tuning the strength of the electric field component of the light wave, one can gain control over this interaction. A simple way of achieving this is by employing microcavities, which are one‐dimensional photonic structures. These give rise to an effective quantization of the light field in one direction. The largest enhancements in the strength of light–matter coupling are achieved for cavities with dimensions on the order of the effective wavelength of light. As organic materials have the very large oscillator strengths required for light–matter coupling, as well as excellent thin film forming properties, they are ideal materials with which to exploit tunable electron–photon coupling. We demonstrate the influence of the optical field strength in organic microcavity photodiodes. Besides allowing tunability of the response spectrum by varying the effective resonator thickness, a large increase in the photocurrent sensitivity is observed below the absorption threshold of the optically active material. The microcavity induced field enhancement plays a particularly important role under two‐photon excitation. In this case we observe a 500‐fold increase in the photocurrent response with respect to a non‐cavity device. This opens up a range of applications for organic microcavity photodiodes as nonlinear detector elements.     

Emerging 0D Transition‐Metal Dichalcogenides for Sensors,Biomedicine, and Clean Energy

Following research on two‐dimensional (2D) transition metal dichalcogenides (TMDs), zero‐dimensional (0D) TMDs nanostructures have also garnered some attention due to their unique properties; exploitable for new applications. The 0D TMDs nanostructures stand distinct from their larger 2D TMDs cousins in terms of their general structure and properties. 0D TMDs possess higher bandgaps, ultra‐small sizes, high surface‐to‐volume ratios with more active edge sites per unit mass. So far, reported 0D TMDs can be mainly classified as quantum dots, nanodots, nanoparticles, and small nanoflakes. All exhibited diverse applications in various fields due to their unique and excellent properties. Of significance, through exploiting inherent characteristics of 0D TMDs materials, enhanced catalytic, biomedical, and photoluminescence applications can be realized through this exciting sub‐class of TMDs. Herein, we comprehensively review the properties and synthesis methods of 0D TMDs nanostructures and focus on their potential applications in sensor, biomedicine, and energy fields. This article aims to educate potential adopters of these excitingly new nanomaterials as well as to inspire and promote the development of more impactful applications. Especially in this rapidly evolving field, this review may be a good resource of critical insights and in‐depth comparisons between the 0D and 2D TMDs.     

2D–Organic Hybrid Heterostructures for Optoelectronic Applications

The unique properties of hybrid heterostructures have motivated the integration of two or more different types of nanomaterials into a single optoelectronic device structure. Despite the promising features of organic semiconductors, such as their acceptable optoelectronic properties, availability of low‐cost processes for their fabrication, and flexibility, further optimization of both material properties and device performances remains to be achieved. With the emergence of atomically thin 2D materials, they have been integrated with conventional organic semiconductors to form multidimensional heterostructures that overcome the present limitations and provide further opportunities in the field of optoelectronics. Herein, a comprehensive review of emerging 2D–organic heterostructures—from their synthesis and fabrication to their state‐of‐the‐art optoelectronic applications—is presented. Future challenges and opportunities associated with these heterostructures are highlighted.     

Recent Developments in Controlled Vapor‐Phase Growth of 2D Group 6 Transition Metal Dichalcogenides

An overview of recent developments in controlled vapor‐phase growth of 2D transition metal dichalcogenide (2D TMD) films is presented. Investigations of thin‐film formation mechanisms and strategies for realizing 2D TMD films with less‐defective large domains are of central importance because single‐crystal‐like 2D TMDs exhibit the most beneficial electronic and optoelectronic properties. The focus is on the role of the various growth parameters, including strategies for efficiently delivering the precursors, the selection and preparation of the substrate surface as a growth assistant, and the introduction of growth promoters (e.g., organic molecules and alkali metal halides) to facilitate the layered growth of (Mo, W)(S, Se, Te)₂ atomic crystals on inert substrates. Critical factors governing the thermodynamic and kinetic factors related to chemical reaction pathways and the growth mechanism are reviewed. With modification of classical nucleation theory, strategies for designing and growing various vertical/lateral TMD‐based heterostructures are discussed. Then, several pioneering techniques for facile observation of structural defects in TMDs, which substantially degrade the properties of macroscale TMDs, are introduced. Technical challenges to be overcome and future research directions in the vapor‐phase growth of 2D TMDs for heterojunction devices are discussed in light of recent advances in the field.     

Fluorescence Enhancement on Large Area Self‐Assembled Plasmonic‐3D Photonic Crystals

Discontinuous plasmonic‐3D photonic crystal hybrid structures are fabricated in order to evaluate the coupling effect of surface plasmon resonance and the photonic stop band. The nanostructures are prepared by silver sputtering deposition on top of hydrophobic 3D photonic crystals. The localized surface plasmon resonance of the nanostructure has a symbiotic relationship with the 3D photonic stop band, leading to highly tunable characteristics. Fluorescence enhancements of conjugated polymer and quantum dot based on these hybrid structures are studied. The maximum fluorescence enhancement for the conjugated polymer of poly(5‐methoxy‐2‐(3‐sulfopropoxy)‐1,4‐phenylenevinylene) potassium salt by a factor of 87 is achieved as compared with that on a glass substrate due to the enhanced near‐field from the discontinuous plasmonic structures, strong scattering effects from rough metal surface with photonic stop band, and accelerated decay rates from metal‐coupled excited state of the fluorophore. It is demonstrated that the enhancement induced by the hybrid structures has a larger effective distance (optimum thickness ≈130 nm) than conventional plasmonic systems. It is expected that this approach has tremendous potential in the field of sensors, fluorescence‐imaging, and optoelectronic applications.     

Merits and Challenges of Ruddlesden–Popper Soft Halide Perovskites in Electro‐Optics and Optoelectronics

Following the rejuvenation of 3D organic–inorganic hybrid perovskites, like CH₃NH₃PbI₃, (quasi)‐2D Ruddlesden–Popper soft halide perovskites R₂A_n?1Pb_nX_3n+1 have recently become another focus in the optoelectronic and photovoltaic device community. Although quasi‐2D perovskites were first introduced to stabilize optoelectronic/photovoltaic devices against moisture, more interesting properties and device applications, such as solar cells, light‐emitting diodes, white‐light emitters, lasers, and polaritonic emission, have followed. While delicate engineering design has pushed the performance of various devices forward remarkably, understanding of the fundamental properties, especially the charge‐transfer process, electron–phonon interactions, and the growth mechanism in (quasi)‐2D halide perovskites, remains limited and even controversial. Here, after reviewing the current understanding and the nexus between optoelectronic/photovoltaic properties of 2D and 3D halide perovskites, the growth mechanisms, charge‐transfer processes, vibrational properties, and electron–phonon interactions of soft halide perovskites, mainly in quasi‐2D systems, are discussed. It is suggested that single‐crystal‐based studies are needed to deepen the understanding of the aforementioned fundamental properties, and will eventually contribute to device performance.     

Electrothermal Control of Graphene Plasmon–Phonon Polaritons

Graphene plasmons are known to offer an unprecedented level of confinement and enhancement of electromagnetic field. They are hence amenable to interacting strongly with various other excitations (for example, phonons) in their surroundings and are an ideal platform to study the properties of hybrid optical modes. Conversely, the thermally induced motion of particles and quasiparticles can in turn interact with electronic degrees of freedom in graphene, including the collective plasmon modes via the Coulomb interaction, which opens up new pathways to manipulate and control the behavior of these modes. This study demonstrates tunable electrothermal control of coupling between graphene mid‐infrared (mid‐IR) plasmons and IR active optical phonons in silicon nitride. This study utilizes graphene nanoribbons functioning as both localized plasmonic resonators and local Joule heaters upon application of an external bias. In the latter role, they achieve up to ≈100 K of temperature variation within the device area. This study observes increased modal splitting of two plasmon–phonon polariton hybrid modes with temperature, which is a manifestation of increased plasmon–phonon coupling strength. Additionally, this study also reports on the existence of a thermally excited hybrid plasmon–phonon mode. This work can open the door for future optoelectronic devices such as electrically switchable graphene mid‐infrared plasmon sources.     

Periodical 2D Photonic–Plasmonic Au/TiOx Nanocavity Resonators for Photoelectrochemical Applications

Effective light trapping at the nanoscale is vital for efficient photoelectrochemical (PEC) applications. Photonic and plasmonic resonators are the two most promising approaches for this purpose, and the synergetic combination of these two resonators will tail the propagation lengths of incident light along with field enhancements, and thus presents further enhanced light‐trapping activity. Herein, a new hybrid photonic–plasmonic resonator is proposed through sputtering plasmonic Au nanoparticles (NPs) into the 2D photonic TiO_x nanocavity. Through facile control of the size of Au NPs, the matching of resonant wavelength of plasmonic Au NPs and photonic nanocavities maximize the light‐trapping intensity and thus further improve the PEC performance. Furthermore, for expanding the PEC applications, after functionalization of Au NPs with aptamer as a biomolecular recognition unit, a PEC aptasensor is also proposed and presents the highest sensitivity for antibiotic detection.     

Tuning Excitonic Properties of Monolayer MoS2 with Microsphere Cavity by High‐Throughput Chemical Vapor Deposition Method

Tuning the optical properties of 2D direct bandgap semiconductors is crucial for applications in photonic light source, optical communication, and sensing. In this work, the excitonic properties of molybdenum disulphide (MoS₂) are successfully tuned by directly depositing it onto silica microsphere resonators using chemical vapor deposition method. Multiple whispering gallery mode (WGM) peaks in the emission wavelength range of ≈650–750 nm are observed under continuous wave excitation at room temperature. Time‐resolved photoluminescence (TRPL) and femtosecond transient absorption (TA) spectroscopy are conducted to study light‐matter interaction dynamics of the MoS₂ microcavities. TRPL study suggests radiative recombination rate of carrier‐phonon scattering and interband transition processes in MoS₂ is enhanced by a factor of ≈1.65 due to Purcell effect in microcavities. TA spectroscopy study shows modulation of the interband transition process mainly occurs at PB‐A band with an estimated F ≈ 1.60. Furthermore, refractive index sensing utilizing WGM peaks of MoS₂ is established with sensitivity up to ≈150 nm per refractive index unit. The present work provides a large‐scale and straightforward method for coupling atomically thin 2D gain media with cavities for high‐performance optoelectronic devices and sensors.     

Nanoparticle‐Enhanced Silver‐Nanowire Plasmonic Electrodes for High‐Performance Organic Optoelectronic Devices

Improved performance in plasmonic organic solar cells (OSCs) and organic light‐emitting diodes (OLEDs) via strong plasmon‐coupling effects generated by aligned silver nanowire (AgNW) transparent electrodes decorated with core–shell silver–silica nanoparticles (Ag@SiO₂NPs) is demonstrated. NP‐enhanced plasmonic AgNW (Ag@SiO₂NP–AgNW) electrodes enable substantially enhanced radiative emission and light absorption efficiency due to strong hybridized plasmon coupling between localized surface plasmons (LSPs) and propagating surface plasmon polaritons (SPPs) modes, which leads to improved device performance in organic optoelectronic devices (OODs). The discrete dipole approximation (DDA) calculation of the electric field verifies a strongly enhanced plasmon‐coupling effect caused by decorating core–shell Ag@SiO₂NPs onto the AgNWs. Notably, an electroluminescence efficiency of 25.33 cd A^?1 (at 3.2 V) and a power efficiency of 25.14 lm W^?1 (3.0 V) in OLEDs, as well as a power conversion efficiency (PCE) value of 9.19% in OSCs are achieved using hybrid Ag@SiO₂NP–AgNW films. These are the highest values reported to date for optoelectronic devices based on AgNW electrodes. This work provides a new design platform to fabricate high‐performance OODs, which can be further explored in various plasmonic and optoelectronic devices.     

Surface Plasmon‐Enhanced Photodetection in Few Layer MoS2 Phototransistors with Au Nanostructure Arrays

2D Molybdenum disulfide (MoS₂) is a promising candidate material for high‐speed and flexible optoelectronic devices, but only with low photoresponsivity. Here, a large enhancement of photocurrent response is obtained by coupling few‐layer MoS₂ with Au plasmonic nanostructure arrays. Au nanoparticles or nanoplates placed onto few‐layer MoS₂ surface can enhance the local optical field in the MoS₂ layer, due to the localized surface plasmon (LSP) resonance. After depositing 4 nm thick Au nanoparticles sparsely onto few‐layer MoS₂ phototransistors, a doubled increase in the photocurrent response is observed. The photocurrent of few‐layer MoS₂ phototransistors exhibits a threefold enhancement with periodic Au nanoarrays. The simulated optical field distribution confirms that light can be trapped and enhanced near the Au nanoplates. These findings offer an avenue for practical applications of high performance MoS₂‐based optoelectronic devices or systems in the future.     

High Spatial Resolution Mapping of Localized Surface Plasmon Resonances in Single Gallium Nanoparticles

Plasmonics has emerged as an attractive field driving the development of optical systems in order to control and exploit light–matter interactions. The increasing interest around plasmonic systems is pushing the research of alternative plasmonic materials, spreading the operability range from IR to UV. Within this context, gallium appears as an ideal candidate, potentially active within a broad spectral range (UV–VIS–IR), whose optical properties are scarcely reported. Importantly, the smart design of active plasmonic materials requires their characterization at high spatial and spectral resolution to access the optical fingerprint of individual nanostructures, attainable by transmission electron microscopy techniques (i.e., by means of electron energy‐loss spectroscopy, EELS). Therefore, the optical response of individual Ga nanoparticles (NPs) by means of EELS measurements is analyzed, in order to spread the understanding of the plasmonic response of Ga NPs. The results show that single Ga NPs may support several plasmon modes, whose nature is extensively discussed.